Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
  • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
  • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
  • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms

Definitions

• the invention relates to an improved process for the preparation of methyl 4 - [(4,5-dihydro-3-methoxy-4-methyl-5-oxo-1H-1,2,4-triazole-1-yl) carbonyl) sulfamoyl] 5-methylthiophene-3-carboxylate (known by the common name "thiencarbazone-methyl").
• a particularly good herbicidal activity have selected substituted thien-3-yl-sulfonylaminocarbonyltriazolinone, such. Thiencarbazone-methyl.
• DE 19933260 AI discloses optional reaction auxiliaries. These relate to such reactions usually usable acid binders.
• the selection mentioned on page 9 of DE 19933260 A1 also includes potassium tert-butylate, as well as basic nitrogen compounds, such as e.g. Amines including tributylamine and
• Pyridines such as 2-methylpyridines, 3-methylpyridine, 5-ethyl-2-methylpyridine, 2,6-dimethylpyridine.
• imidazoles are not mentioned in DE 19933260 AI as reaction auxiliaries.
• Document DE 10 2004 063192 A1 describes the preparation of the sulfonyl isocyanate using the process alternative disclosed in DE 19933260 A1 (ie preparation of thiencarbazone-methyl by reacting sulfonyl isocyanates with 5-methoxy-4-methyl-2,4-dihydro-3H l, 2,4-triazol-3-one) proposed a method starting from sulfonamide and phosgene.
• the object of the invention is to provide an improved process for the preparation of substituted thien-3yl-sulfonylamino-carbonyltriazolinones, in particular of thiencarbazone-methyl, i. the compound of formula (I), wherein the improved process is intended to enable the preparation of the target compound thiencarbazone-methyl in a high purity and yield.
• radical R 1 is an unsubstituted (C 1 -C 12) -alkyl or an unsubstituted benzyl.
• the above reaction scheme shows that when the reaction is carried out as a one-pot synthesis at the beginning of the reaction, a 4-component system is present.
• the starting material is 5-methoxy-4-methyl-2,4-dihydro-3H-l, 2,4-triazol-3-one of the formula (IV) only after formation of the sulfonyl isocyanate from compounds of the formulas ( II) and (III) are added to the mixture in the presence of an N-alkylimidazole of the formula (V).
• the unexpected selectivity of the reaction shown in the scheme is that the triazolinone (IV) reacts with thiencarbazone-methyl only after formation of the sulfonyl isocyanate with it.
• metal cyanates are strong bases (eg, sodium cyanate (NaOCN) has a pH of 10).
• NaOCN sodium cyanate
• metal cyanates act as O-nucleophiles.
• the O-nucleophilicity of the metal cyanates used according to the invention does not affect the course of the present reaction, ie its yield and its selectivity.
• Carboxylic acid halides are to be regarded.
• inorganic bases such as K 2 CO 3 or potassium tert-butoxide (KOtBut) which have also proved to be unsuitable.
• the process according to the invention is preferably carried out in the presence of an imidazole of the formula (V) in which the radical R 1 is an unsubstituted (C 1 -C 6) -alkyl or an unsubstituted benzyl.
• an imidazole of the formula (V) in which the radical R 1 is a substituted (C 1 -C 6) -alkyl or a substituted benzyl is not preferred, is likewise within the scope of the invention.
• Unbranched (Ci-C i) -alkyl, i. Methyl, ethyl, n-propyl or n-butyl for Ri are most preferred.
• N-methylimidazole i. when the radical Ri in formula (V) is methyl.
• the reagents are preferably employed in equimolar amounts or in excess in the process according to the invention.
• Me in compounds of the formula MeOCN (III) is Na or K.
• the most preferred metal cyanate in the process according to the invention is NaOCN.
• the process is carried out in an organic solvent, nonpolar and polar solvents being suitable.
• non-polar solvents are toluene, chlorobenzene, xylene, methyl tert-butyl ether,
• Particularly preferred polar solvents are selected from the group consisting of acetonitrile, butyronitrile, tetrahydrofuran (THF), methyl THF, dimethoxyethane, sulfolane, dimethylformamide and dimethylacetamide.
• Most preferred solvents are acetonitrile and THF.
• reaction of the starting materials in a temperature range of 20 ° to 110 ° over a period (reaction time, reaction time) of 3 hours to 24 hours.
• the reaction of the starting materials in a temperature range of 30 ° to 90 °. Most preferably, the reaction of the reactants takes place in a temperature range of 50 ° to 80 °.
• Another aspect of the invention relates to the use of an imidazole of the formula (V)
• radical Ri represents a unsubstitutêts (Ci-Ci 2) -alkyl or a unsubstitutêts benzyl, for the preparation of the compound of formula (I)
• the production process according to the invention can be carried out as a one-pot process or as a two-stage reaction.
• the active ingredient or its salt precipitates out of the reaction mixture and can easily be filtered off. It is particularly advantageous at the end of the reaction to use an inorganic base such as e.g. LiOH, K2CO3, NaHCu3, NaOH, Na2Cu3, CaCC or KOH are added to the mixture to isolate the drug as insoluble Li, Na, K or Ca salt. Preferred is the use of NaHCC.
• the amount of base to be used depends on how much metal cyanate when carrying out the
• the active ingredient is released and isolated after filtration.
• an acid e.g., HCl, H2SO4
• the isocyanate can be isolated and purified by distillation in vacuo.
• Precipitate was filtered off and washed with 50 ml of acetonitrile. Thereafter, the precipitate was washed with 70 ml of 20% H 2 S0 4 , 100 ml of hot (70 ° C) water and 50 ml of acetone and dried at 50 ° C. This gave 31.4 g of methyl 4 - [(4,5-dihydro-3-methoxy-4-methyl-5-oxo-1H-l, 2,4-triazole-1-yl) carbonyl) sulfamoyl] -5 Methylthiophene-3-carboxylate, 79% of theory with a purity of 98%.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Plural Heterocyclic Compounds (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2018
  • 2018-02-13 TW TW107105126A patent/TWI668211B/zh not_active IP Right Cessation
  • 2018-02-15 KR KR1020197024548A patent/KR102520302B1/ko active IP Right Grant
  • 2018-02-15 BR BR112019017396-0A patent/BR112019017396B1/pt active IP Right Grant
  • 2018-02-15 WO PCT/EP2018/053771 patent/WO2018153767A1/de unknown
  • 2018-02-15 ES ES18706467T patent/ES2857821T3/es active Active
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• 2019
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